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Abstract Aldehyde‐assisted water electrolysis offers an attractive pathway for energy‐saving bipolar hydrogen production with combined faradaic efficiency (FE) of 200% while converting formaldehyde into value‐added formate. Herein we report the design and synthesis of noble metal‐free Cu₆Sn₅alloy as a highly effective electrocatalyst for formaldehyde electro‐oxidative dehydrogenation, demonstrating a geometric current density of 915 ± 46 mA cm⁻²at 0.4 V versus reversible hydrogen electrode, outperforming many noble metal electrocatalysts reported previously. The formaldehyde‐assisted water electrolyzer delivers 100 mA cm⁻²at a low cell voltage of 0.124 V, and a current density of 486 ± 20 mA cm⁻²at a cell voltage of 0.6 V without any iR compensation and exhibits nearly 200% faradaic efficiency for bipolar hydrogen production at 100 mA cm⁻²in 88 h long‐term operation. Density functional theory calculations further confirm the notably lowered barriers for dehydrogenation and Tafel steps on the Cu₆Sn₅ surface compared to Cu, underscoring its potential as a highly active catalyst.